The present invention relates to compositions of matter, which may be used to purify industrial waste water and other industrial waste liquids, solids or semiliquids, chemicals, demulsification processes, in the paper industry (for sizing processes, drainage, retention, flotation), miniming industry, clay industry or other industries which have a waste water or waste liquid problem.
It is well known that guanidine resins or polymers are of lower molecular weight, and have very limited shelf life, in most cases less than 3 months, often only a few days or weeks. Low cationic charge polymers are of limited use in industrial water treatment of potable water. Treatment is very limited, since the free formaldehyde content is high. Most of the products can be used only as coagulants in connection with alum, AlCl.sub.3, FeCl.sub.3, Fe.sub.2 (SO.sub.4).sub.3 and mixtures of these, at a pH of from 6.0 to 9.0.
It has been found that reaction of guanidine, guanidine polymers or guanidine alkylamine/alkylamine polymers with inorganic adduct polymers and/or its guanidine derivative polymers alloy with organic alkyl or alkylene polyamine and adducts with inorganic adducts polymers will form very stable multi cationic or anionic polymers which can be used as coagulant and coagulant-flocculants with or without any electrolytes from a pH of 2 to a pH of 13.5.
These products can be used in any kind of industrial waste water, potable water, acid rain water purification, sludge coagulation and solidifications, or dust suppressant applications.
The inorganic-organic adduct polymers are twice as efficient as regular guanidine resins, having a shelf life from at least one year to four years, depending on the composition. The products produce low volume sludges, which relieve large volume disposal problems for the environment.
The invented compositions are made from inorganic polymers in reaction with guanidine polymers and their organic alloy with high nitrogen content compositions of polyamines, polyquaternized polymers, polyamides, and polyamine-polyamide polymers.
This invention generally relates to the novel of inorganic-organic alloy (co)polymers of the formula: ##STR1## where: Me.sub.m.sup.II is a divalent cation group selected from Mg, Zn, Ca, Fe.sup.2+, and m=0 to 5;
Me.sub.n.sup.III is a tri- or more valent metal, preferably Fe or Al, and n=1 to 20; PA0 Aci is selected from the monovalent anionic group of (a) Cl, (b) Br, (c) I.sup.-, (d) NO.sub.3.sup.-, (e) CH.sub.3 COO.sup.-, and (f) a mixture of these (preferably Aci is Cl.sup.-); PA0 PAM, PAD and PQAM stand for polyamine, polyamide and polyquaternized polymers; PA0 p=0 to 75; PA0 y=0 to 15; PA0 x=preferably 0 to 95% by weight in compositions; PA0 z=percentage by weight of the polyamine in the alloy composition, which can vary from 0 to 95%; PA0 t=percentage by weight of the polyamide, which can vary from 0 to 95%; PA0 t+z=percentage by weight of the mixture of polyamide-polyamine, which can vary in compositions from 0% to 95% by weight; PA0 w=percentage by weight of the quaternary ammonium and/or allyltrialkylammonium compounds, which can vary from 0 to 95%; 2m+3n&gt;2y+p; z&gt;t PA0 R.sub.1 --refers to the bridge cationic and/or multiple organic cationic charges which can vary from 0% to 28% by weight; PA0 R.sub.2 --refers to the alkyl phosphonic acid esters, and or amine derivatives which will form phosphammonium cationic charge groups, which can vary from 0 to 28% by weight. PA0 Me.sub.m.sup.II is a divalent cation group selected from Mg, Zn, Ca, Fe.sup.2+ and m=0 to 5; PA0 Me.sub.n.sup.III is a tri- or more valent metal, preferably Fe or Al, and n-1 to 20; PA0 Aci is selected from a monovalent anionic group consisting of (a) Cl.sup.- (b) Br.sup.-, (c) I.sup.-, (d) NO.sub.3.sup.-, (e) CH.sub.3 COO.sup.- or (f) a mixture of two or more of the foregoing, but preferably Aci is Cl.sup.-. PA0 X is sodium or potassium aluminate PA0 k, m, n are positive numbers EQU Al.sub.1-x Fe.sub.x.sup.III Fe.sub.y.sup.II (OH).sub.3+2y-2 (Hal).sub.z I(c) PA0 Hal=chlorine, bromine, iodine, or a mixture thereof; PA0 (x+y)/(1-x)=about 0.2 to 1.5, PA0 z&lt;3+2y, and PA0 (3+2y-2)/(3+2y)=about 0.24 to 0.67. EQU Al.sub.m (OH).sub.x (SO.sub.4).sub.y (H.sub.2 PO.sub.4).sub.z I(d) PA0 m, n are positive integers PA0 M.sub.n e is a tri- or more valent metal PA0 X is Cl.sup.-, CH.sub.3 COO.sup.-, or NO.sub.3. PA0 1. Polyhydroxyaluminumchloride: EQU Al.sub.4 (OH).sub.9 (Cl).sub.3, or Al.sub.8 (OH).sub.2 (Cl).sub.3, or Al.sub.11 (OH).sub.30 (Cl).sub.3 ; PA0 2. Hydroxyaluminumchloride: Al.sub.2 (OH).sub.5 Cl as ChlorhydrolTR-50, AstrigenTR-50; PA0 3. Polyhydroxyaluminumagnesiumchloride: Al.sub.3 Mg (OH).sub.9 (Cl).sub.2 ; PA0 4. Polyhydroxyaluminumcalciumchloride: Al.sub.7 Ca.sub.0.04 (OH).sub.17.01 (Cl).sub.4 ; PA0 5. Polyhydroxyaluminumagnesiumsulfate: Al.sub.4 Mg(OH).sub.4 (SO.sub.4).sub.3.5 ; PA0 6. Hydroxyaluminum sulfate: Al.sub.2 (OH).sub.4 (SO.sub.4); PA0 7. Polyhydroxyaluminumzincoxidechloride: Al.sub.3 (OH).sub.3 ZnO(OH)(Cl).sub.5 ; PA0 8. Polyhydroxyaluminum and/or magnesiumchlorosulfate: EQU Al.sub.4 (OH).sub.6 (Cl).sub.4 (SO.sub.4); EQU Al.sub.4 Mg (OH).sub.6 (Cl).sub.4 (SO.sub.4).sub.2 ; or EQU Al.sub.3 Mg (OH).sub.6 (Cl).sub.3 (SO.sub.4); PA0 9. Polyaluminumferic and/or ferrous chloride; ##STR2## 10. Polyaluminumchloridesulfate; and 11. Polyhydroxyaluminumchloro silicate. PA0 R.sub.2 refers to the alkyl phosphonic acid ester and/or amine derivatives of phosphonic acid, which will form the phosphonium cationic charge groups, from 0 to 28% bw of the composition. ##STR5## wherein: in B(2): R.sub.1 refers to the bridge cationic charge and/or multiple organic cationic charges of mixture of thereof, such as but not limited to: ##STR6## In B(3): R.sup.2 refers to the dialkyl hydrogen phosphite, ester amines, phosphorus acid and its esters or salts, H.sub.3 PO.sub.4 and its salts, such as sodium dihydrogen phosphates, including the following: PA0 (a) dimethyl hydrogen phosphite; PA0 (b) hydroxyethylidene-1,1-diphosphonic acid and its salts (of Li, Na, K, and NH.sub.4) PA0 (c) diethylenetriaminepentmethylene phosphonic acid and its salts (Li, Na, K, NH.sub.4) PA0 (d) carbonyl diamidetetramethylene phosphonic acid and its salts (Li, Na, K, NH.sub.4) PA0 (e) N(2-aminoethyl piperazine) phosphonic acid and its salts (Li, Na, K, NH.sub.4) PA0 (f) N(2-aminoethylmorpholine) phosphonic acid and its salts (Li, Na, K, NH.sub.4) PA0 (g) 2 (heptyl-2-imidazoline) phosphonic acid and its salts (Li, Na, K, NH.sub.4) PA0 (h) phosphoric acid and its salts, such as sodiumdihydrogenphosphate, PA0 (i) methylene phosphonic acid substituted amide&gt;N--CH.sub.2 PO.sub.3 H.sub.2 made from Urea (U)-Formaldehyde (F)-phosphorus acid and/or mixture of phosphorus acid/hydrochloric acid where the HCl is used as a catalyst from 0.25 to 0.5 mole, the mole ratio of U--CH.sub.2 O--H.sub.3 PO.sub.3 being 1:3.50:3.25. PA0 (B): PA0 0.356-2.0; 0.490-5.0; 0.5-2.0 PA0 0.5-4.0; 1.5-9.0; 0.3-2.0; 0.05-0.5 PA0 1.0-2; 2-4; 1-2 PA0 5-95% by weight of inorganic polymers PA0 0-95% by weight guanidine polymers, and/or PA0 5-95% by weight of inorganic polymers PA0 70-0% by weight of guanidine polymers PA0 0-95% by weight of polyamine and/or polyamide/polyamine, and/or polyamide. PA0 0% to 95% of polyamine and/or polyamide/polyamine, and/or polyamide. PA0 95% to 5% of inorganic polymers, quaternary ammonium and/or allyltrialkylammonium compounds.
The invented compositions of matter are useful to purify industrial waste water (w.w.) and other industrial waste liquids, solids or semiliquids, from chemical plants, demulsification processes, paper industry (such as sizing processes, drainage, retention, flotation), mining industry, and clay industries.